EP3715405B1 - Faserverstärktes formmaterial und formkörper damit - Google Patents

Faserverstärktes formmaterial und formkörper damit Download PDF

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Publication number
EP3715405B1
EP3715405B1 EP18879026.5A EP18879026A EP3715405B1 EP 3715405 B1 EP3715405 B1 EP 3715405B1 EP 18879026 A EP18879026 A EP 18879026A EP 3715405 B1 EP3715405 B1 EP 3715405B1
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EP
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Prior art keywords
fiber
molding material
resin
reinforced molding
polyisocyanate
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EP18879026.5A
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English (en)
French (fr)
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EP3715405A4 (de
EP3715405A1 (de
Inventor
Chikara Yoshioka
Yukiko Fujita
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DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Publication of EP3715405A4 publication Critical patent/EP3715405A4/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/06—Unsaturated polyesters
    • C08J2367/07—Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret

Definitions

  • the present invention relates to a fiber-reinforced molding material from which a molded article excellent in various physical properties can be obtained, and a molded article thereof.
  • a fiber-reinforced resin composite material obtained by reinforcing a thermosetting resin such as an epoxy resin or an unsaturated polyester resin using carbon fibers as reinforcing fibers has attracted attention because of its characteristics of excellent heat resistance and mechanical strength while being lightweight, and has been increasingly used for various structural applications such as casings of automobiles and airplanes or various members .
  • an autoclave method in which a material called prepreg is heated and cured in a pressurizable autoclave is known, and as a method for molding a material using an unsaturated polyester resin, a method in which an intermediate material called sheet molding compound (SMC) or bulk molding compound (BMC) is cured and molded by a method such as press molding or injection molding is known.
  • SMC sheet molding compound
  • BMC bulk molding compound
  • a molding material for example, a carbon fiber-reinforced sheet-shaped molding material containing an unsaturated polyester, a vinyl monomer, a thermoplastic polymer, a polyisocyanate, a filler, conductive carbon black, and a wide carbon fiber bundle as essential components is known (for example, see PTL 1).
  • a molded article excellent in appearance can be obtained from this molding material, since a styrene monomer having high volatility is used, the odor is strong, and there is a problem in the working environment during the molding operation.
  • composition for a fiber-reinforced composite material comprises (A) 100 parts by mass of a resin or mixed resin containing a radically polymerizable unsaturated group and an epoxy group, (B) 0-200 parts by mass of a radically polymerizable monomer and/or an epoxy diluent, (C) 0.5-200 parts by mass of a curing agent, (D) 5-2,000 parts by mass of a reinforced fiber and (E) 0-200 parts by mass of a thickener.
  • EP 3 438 167 A1 describes a fiber-reinforced molding material including as essential materials: a vinyl ester (A) that is a reaction product of an epoxy resin (a1) having an epoxy equivalent in the range of 180 to 500 and (meth) acrylic acid (a2); an unsaturated monomer (B) having a flash point of 100°C or higher; a polyisocyanate (C); a polymerization initiator (D); and carbon fibers (E) having a fiber length of 2.5 to 50 mm, in which the mass ratio ((A)/(B)) of the vinyl ester (A) to the unsaturated monomer (B) is in the range of 40/60 to 85/15, and the molar ratio (NCO/OH) of isocyanate groups (NCO) in the polyisocyanate (C) to hydroxy groups (OH) in the vinyl ester (A) is in the range of 0.25 to 0.85.
  • a vinyl ester (A) that is a reaction product of an epoxy resin (a1) having an
  • DATABASE WPI, Week 201562 2015 Thomson Scientific, London, GB; AN 2015-53971Q & WO 2015/133289 A1 11 September 2015 describe a molding material for heat compression molding, the molding material being obtained by impregnating a carbon fiber reinforcing material (B) with a resin composition (A) that contains a polymethacrylate compound (a1) that has a hydroxyl group, a polyisocyanate compound (a2), and a polymerization initiator (a3), the molding material for heat compression molding being characterized in that the carbon fiber reinforcing material (B) is a carbon paper that is surface treated with a water-soluble resin (b1) that has a hydroxyl group.
  • JP 2009 013306 A describes a carbon fiber reinforced sheeted molding material comprises an unsaturated polyester (a), a vinyl monomer (b), a thermoplastic polymer (c), a polyisocyanate (d), a filler (e), an electroconductive carbon black (f) and a broad carbon fiber bundle (g) as essential components.
  • the molding material comprises the thermoplastic polymer (c) of 10-30 mass%, the polyisocyanate (d) of 0.3-5 mass%, the electroconductive carbon black (f) of 1-12 mass% based on the total amount of (a) - (c) of 100 mass%, and the broad carbon fiber bundle (g) of 10-35 mass% based on the total amount of (a)-(g) of 100 mass%.
  • WO 2017/043325 A1 describes a heat-compression-molding molding material containing a resin composition (A) and a carbon-fiber-reinforced member (B), wherein the heat-compression-molding molding material is characterized in that the resin composition (A) contains a hydroxyl-group-containing poly(meth)acrylate compound (a1), a radical-polymerizable diluent (a2), a polyisocyanate compound (a3), a styrene elastomer (a4) having an unsaturated double bond, and a polymerization initiator (a5); and the carbon-fiber-reinforced member (B) is carbon paper surface-treated with a hydroxyl-group-containing water soluble resin (b1).
  • the resin composition (A) contains a hydroxyl-group-containing poly(meth)acrylate compound (a1), a radical-polymerizable diluent (a2), a polyisocyanate compound (a3),
  • WO 2017/110446 A1 discloses a prepreg having as essential components a urethane-modified epoxy (meth)acrylate (A), which is the reaction product of an epoxy (meth) acrylate (a1) having an average number of hydroxyl groups of 1.8-2.6 and a polyisocyanate (a2) having an average number of isocyanate groups of 2-3, an ethylenic unsaturated monomer (B), a polymerization initiator (C), and reinforcing fibers (D), the prepreg being characterized in that the molar ratio (NCO/OH) of the isocyanate groups (NCO) of the polyisocyanate (a2) and the hydroxyl groups (OH) of the epoxy (meth)acrylate (a1) is 0.6-1.1, and the proportion of the ethylenic unsaturated monomer (B) in the total mass of the epoxy (meth) acrylate (a1) and ethylenic unsaturated monomer (B) is 10-50 mass%.
  • An object of the present invention is to provide a fiber-reinforced molding material excellent in a working environment during the molding operation and capable of obtaining a molded article excellent in various physical properties such as dimensional accuracy, and to provide the molded article.
  • a fiber-reinforced molding material including, as essential components, a specific vinyl ester, an unsaturated monomer having a flashpoint of 100°C or higher, a polymerization initiator, a thermoplastic resin, a polyisocyanate, and carbon fibers having a fiber length of 2.5 to 50 mm is excellent in handling property and molding property, and a molded article excellent in various physical properties such as dimensional accuracy can be obtained, and have completed the present invention.
  • the present invention provides a fiber-reinforced molding material including: as essential raw materials, a vinyl ester (A) which is a reaction product of an epoxy resin (a1) having an epoxy equivalent of 180 to 500 and a (meth)acrylic acid (a2); an unsaturated monomer (B) having a flash point of 100°C or higher; a thermoplastic resin (C); a polyisocyanate (D); a polymerization initiator (E); and carbon fibers (F) having a fiber length of 2.5 to 50 mm, wherein the thermoplastic resin (C) has a solubility in the unsaturated monomer (B) at 23°C being 1 g/100 g or less, the mass ratio ((A)/(B)) of the vinyl ester (A) to the unsaturated monomer (B) is in the range of 40/60 to 85/15, and the molar ratio (NCO/OH) of the isocyanate group (NCO) of the polyisocyanate (D) to the hydroxy group
  • Molded articles obtained from the fiber-reinforced molding material of the present invention are excellent in dimensional moldability and the like, and thus are suitable for use in automotive members, railroad vehicle members, airspace craft members, ship members, house facility members, sports members, light-weight vehicle members, construction and civil engineering members, case bodies for OA instrument, and the like.
  • a fiber-reinforced molding material of the present invention includes, as essential raw materials, a vinyl ester (A) which is a reaction product of an epoxy resin (a1) having an epoxy equivalent in the range of 180 to 500 and a (meth)acrylic acid (a2); an unsaturated monomer (B) having a flash point of 100°C or higher; a thermoplastic resin (C); a polyisocyanate (D); a polymerization initiator (E); and carbon fibers (F) having a fiber length of 2.5 to 50 mm, wherein the thermoplastic resin (C) has a solubility in the unsaturated monomer (B) at 23°C being 1 g/100 g or less, the molar ratio (COOH/EP) of the epoxy group (EP) of the epoxy resin (a1) to the carboxyl group (COOH) of the (meth)acrylic acid (a2) is in the range of 0.6 to 1.1, the mass ratio ((A)/(B)) of the vinyl ester (A) to the
  • (meth)acrylic acid refers to one or both of acrylic acid and methacrylic acid.
  • the vinyl ester (A) is obtained by reacting the epoxy resin (a1) having an epoxy equivalent in the range of 180 to 500 with the (meth)acrylic acid (a2). Since the vinyl ester (A) contains a molecular chain having 2 or more hydroxy groups per molecular chain, the reaction is preferably carried out at a molar ratio (COOH/EP) in the range of 0.6 to 1.1 because the fiber-reinforced molding material of the present invention reacted with an aromatic isocyanate is excellent in the balance between handling property such as film peelability and tackiness during molding and fluidity. From this viewpoint, the epoxy equivalent of the epoxy resin (a1) is more preferably in the range of 200 to 400.
  • Examples of the epoxy resin (a1) include bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol fluorene type epoxy resins, and biscresol fluorene type epoxy resins; novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; glycidyl ethers of polyhydric alcohols such as oxazolidone-modified epoxy resins, glycidyl ethers of phenols such as brominated epoxy resins of these resins, dipropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl ethers of alkylene oxide adducts of bisphenol A, and diglycidyl ethers of hydrogenated bisphenol A; alicyclic epoxy resins such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclo hexane
  • a bifunctional aromatic epoxy resin is preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are more preferable, because they are excellent in the strength of a molded article, the handling property of a molding material, and the fluidity of a molding material during molding.
  • These epoxy resins may be used alone or in combination of two or more kinds thereof.
  • the epoxy equivalent of the epoxy resins (a1) is the average epoxy equivalent of all epoxy resins.
  • the molecular weight of the epoxy resin (a1) may be increased by a dibasic acid such as bisphenol A and then used.
  • the reaction between the epoxy resin and the (meth) acrylic acid described above is preferably carried out at 60 to 140°C using an esterification catalyst.
  • an esterification catalyst it is also possible to use a polymerization inhibitor or the like.
  • the unsaturated monomer (B) has a flash point of 100°C or higher. This makes it possible to suppress the odor during the molding operation, and to improve the working environment. In addition, since the boiling point of the unsaturated monomer is high, molding property during high-temperature molding is excellent, high-temperature short-time molding is possible, and productivity is improved.
  • the flash point in the present invention is a flash point measured by the Cleveland open-cup method defined in JIS K2265-4:2007.
  • Examples of the unsaturated monomer (B) include monofunctional (meth)acrylate compounds such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate alkyl ether, polypropylene glycol (meth)acrylate alkyl ether, 2-ethylhexyl methacrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isotridecyl (meth)acrylate, n-stearyl (meth)acrylate, tetrahydrofurfuryl methacrylate, isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentanyl methacrylate; di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,
  • aromatic unsaturated monomers are preferable, and benzyl methacrylate and phenoxyethyl methacrylate are more preferable, because a molding material having higher strength can be obtained.
  • These unsaturated monomers may be used alone or in combination of two or more kinds thereof.
  • the mass ratio ((A)/(B)) of the vinyl ester (A) to the unsaturated monomer (B) is in the range of 40/60 to 85/15, and is preferably in the range of 50/50 to 70/30 because the balance between the resin impregnation property into the carbon fiber, the handling property (tackiness), and the curing property is further improved.
  • the viscosity of the mixture of the vinyl ester (A) and the unsaturated monomer (B) is preferably in the range of 200 to 8000 mPa ⁇ s (25°C) because the resin impregnating property into the carbon fiber is further improved.
  • thermoplastic resin (C) examples include polyamide resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polycarbonate resins, urethane resins, polypropylene resins, polyethylene resins, polystyrene resins, acrylic resins, polybutadiene resins, polyisoprene resins, and copolymers such as styrene-divinylbenzene copolymers and styrene-butadiene copolymers. These thermoplastic resins may be used alone or in combination of two or more kinds thereof.
  • thermoplastic resin (C) it is preferable to use a powdery thermoplastic resin because the warpage deformation of the obtained molded article can be further reduced, and a solubility in the unsaturated monomer (B) at 23°C is 1 g/100 g or less, and more preferably 0.1 g/100 g or less.
  • the content of the thermoplastic resin (C) is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 40% by mass, and still more preferably in the range of 10 to 30% by mass, with respect to the total amount of the vinyl ester (A) and the unsaturated monomer (B), because the warpage deformation is small and a high-strength molded article is obtained.
  • polyisocyanate (D) examples include aromatic polyisocyanates such as diphenylmethane diisocyanate (4,4'-form, 2,4'-form, or 2,2'-form, or a mixture thereof), modified product of diphenylmethane diisocyanate including carbodiimide modified product, nurate modified product, biurette modified product, or urethane imine modified product of diphenylmethane diisocyanate, and polyol modified product which is modified from polyol with number average molecular weight of 1,000 or less such as diethylene glycol and dipropylene glycol, tolylene diisocyanate, tolidine diisocyanate, polymethylene polyphenyl polyisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, and tetramethylxylene diisocyanate; alicyclic polyisocynates such as isophorone diisocyanate, hydrogenated diphen
  • aromatic polyisocyanates are preferable, and carbodiimide modified products of diphenylmethane diisocyanate are more preferable, since molding materials excellent in handling property (film peelability and tackiness) can be obtained.
  • the carbodiimide modified product of diphenylmethane diisocyanate include products having a urethane imine structure formed by adding an isocyanate group to a carbodiimide group, in addition to products having a carbodiimide group.
  • These polyisocyanates (D) may be used alone or in combination of two or more kinds thereof.
  • the molar ratio (NCO/OH) of the isocyanate group (NCO) of the polyisocyanate (D) to the hydroxy group (OH) of the vinyl ester (A) is 0.25 to 0.85, and is preferably 0.5 to 0.8 because the balance between the handling property (film peelability and tackiness) due to the increase in molecular weight and the resin fluidity during molding is more excellent.
  • the polymerization initiator (E) is not particularly limited, but is preferably an organic peroxide, and examples thereof include a diacyl peroxide compound, a peroxyester compound, a hydroperoxide compound, a ketone peroxide compound, an alkyl perester compound, a percarbonate compound, and a peroxyketal, and can be appropriately selected depending on the molding conditions. These polymerization initiators (E) may be used alone or in combination of two or more kinds thereof.
  • a polymerization initiator having a temperature of 70°C or higher and 110°C or lower for obtaining a 10-hour half-life is preferably used for the purpose of shortening the molding time.
  • the temperature is 70°C or higher and 110°C or lower, the life of the fiber-reinforced molding material at normal temperature is long, and the fiber-reinforced molding material can be cured in a short time by heating, which is preferable, and the balance between the curing property and the molding property is more excellent.
  • Examples of such a polymerization initiator include 1,6-bis(t-butylperoxycarbonyloxy)hexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, t-butylperoxydiethyl acetate, t-butylperoxyisopropyl carbonate, t-amylperoxyisopropyl carbonate, t-hexylperoxyisopropyl carbonate, di-tert-butylperoxyhexahydroterephthalate, and t-amylperoxytrimethylhexanoate.
  • the content of the polymerization initiator (E) is preferably in the range of 0.3 to 3% by mass with respect to the total amount of the vinyl ester (A) and the unsaturated monomer (B) because both curing characteristics and storage stability are excellent.
  • carbon fibers (F) carbon fibers cut into lengths of 2.5 to 50 mm are used, and carbon fibers cut into lengths of 5 to 40 mm are more preferable because the fluidity in the mold during molding, the appearance of the molded article, and the mechanical properties are further improved.
  • carbon fibers (F) various types of carbon fibers such as polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, and rayon-based carbon fibers can be used.
  • polyacrylonitrile-based carbon fibers are preferable because high-strength carbon fibers can be easily obtained.
  • the number of filaments of the fiber bundle used as the carbon fibers (F) is preferably 1000 to 60000 from the viewpoint of further improving the resin impregnation property and the mechanical properties of the molded article.
  • the content of the carbon fibers (F) in the components of the fiber-reinforced molding material of the present invention is preferably in the range of 25 to 80% by mass, more preferably in the range of 40 to 70% by mass, from the viewpoint of further improving the mechanical properties of the obtained molded article.
  • the carbon fiber content is low, there is a possibility that a high-strength molded article cannot be obtained, and when the carbon fiber content is high, there is a possibility that the resin impregnation property into the fiber is insufficient, the molded article swells, and a high-strength molded article cannot be obtained.
  • the carbon fibers (F) in the fiber-reinforced molding material of the present invention are impregnated with the resin in a state in which the fiber direction is random.
  • the fiber-reinforced molding material of the present invention may contain components other than the vinyl ester (A), the unsaturated monomer (B), the thermoplastic resin (C), the polyisocyanate (D), the polymerization initiator (E), and the carbon fibers (F).
  • a thermosetting resin other than the vinyl ester (A) a thermoplastic resin, a polymerization inhibitor, a curing accelerator, a filler, a shrinkage reducing agent, a release agent, a viscosity improver, a viscosity reducing agent, a pigment, an antioxidant, a plasticizer, a flame retardant, an antibacterial agent, an ultraviolet stabilizer, a reinforcing material, a photo-curing agent, and the like may be contained.
  • thermosetting resin examples include a vinyl urethane resin, an unsaturated polyester resin, an acrylic resin, an epoxy resin, a phenol resin, a melamine resin, and a furan resin. These thermosetting resins may be used alone or in combination of two or more kinds thereof.
  • thermoplastic resin examples include a polyamide resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polycarbonate resin, a urethane resin, a polypropylene resin, a polyethylene resin, a polystyrene resin, an acrylic resin, a polybutadiene resin, a polyisoprene resin, and resins obtained by modifying these resins by copolymerization or the like. These thermoplastic resins may be used alone or in combination of two or more kinds thereof.
  • polymerization inhibitor examples include hydroquinone, trimethylhydroquinone, p-t-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, and copper chloride. These polymerization inhibitors may be used alone or in combination of two or more kinds thereof.
  • curing accelerator examples include metal soaps such as cobalt naphthenate, cobalt octenoate, vanadyl octenoate, copper naphthenate, and barium naphthenate; and metal chelate compounds such as vanadyl acetylacetate, cobalt acetylacetate, and iron acetylacetonate.
  • metal soaps such as cobalt naphthenate, cobalt octenoate, vanadyl octenoate, copper naphthenate, and barium naphthenate
  • metal chelate compounds such as vanadyl acetylacetate, cobalt acetylacetate, and iron acetylacetonate.
  • amines examples include N,N-dimethylamino-p-benzaldehyde, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, and diethanolaniline.
  • These curing accelerators may be used alone or in combination of two or more kinds thereof.
  • Examples of the filler include inorganic compounds and organic compounds, which can be used for adjusting physical properties such as strength, elastic modulus, impact strength, and fatigue durability of the molded article.
  • Examples of the inorganic compound include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, barite, baryta, silica, silica sand, dolomite limestone, gypsum, aluminum fine powder, hollow balloons, alumina, glass powder, aluminum hydroxide, white marble, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, and iron powder.
  • Examples of the organic compound include natural polysaccharide powder such as cellulose and chitin, and synthetic resin powder.
  • synthetic resin powder include organic powder composed of hard resin, soft rubber, elastomer, or polymer (copolymer) or the like, and particles having a multilayer structure such as a core-shell structure. Specific examples thereof include particles made of butadiene rubber and/or acrylic rubber, urethane rubber, silicon rubber, and the like, polyimide resin powder, fluororesin powder, and phenol resin powder. These fillers may be used alone or in combination of two or more kinds thereof.
  • release agent examples include zinc stearate, calcium stearate, paraffin wax, polyethylene wax, and carnauba wax. Preferred examples thereof include paraffin wax, polyethylene wax, and carnauba wax. These release agents may be used alone or in combination of two or more kinds thereof.
  • viscosity improver examples include metal oxides and metal hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide, and acrylic resin-based fine particles, which can be appropriately selected depending on the handling property of the fiber-reinforced molding material of the present invention. These viscosity improvers may be used alone or in combination of two or more kinds thereof.
  • the fiber-reinforced molding material of the present invention is preferably a sheet molding compound (hereinafter, abbreviated as "SMC") or a bulk molding compound (hereinafter, abbreviated as "BMC”) from the viewpoint of excellent productivity and molding property having design diversity.
  • SMC sheet molding compound
  • BMC bulk molding compound
  • Examples of the method for producing the SMC include a method in which the components such as the vinyl ester (A), the unsaturated monomer (B), the thermoplastic resin (C), the polyisocyanate (D), and the polymerization initiator (E) are mixed and dispersed using a mixer such as an ordinary mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder, the obtained resin composition is applied to carrier films placed above and below so as to have a uniform thickness, the carbon fibers (F) are sandwiched between the resin compositions on the carrier films placed above and below, and then the whole is passed between impregnation rolls to impregnate the carbon fibers (F) with the resin compositions by applying pressure, and then the whole is wound into a roll shape or folded in a zigzag manner.
  • a mixer such as an ordinary mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder
  • a polyethylene film, a polypropylene film, a laminate film of polyethylene and polypropylene, polyethylene terephthalate, nylon or the like may be used.
  • Examples of the method for producing the BMC include a method in which the components such as the vinyl ester (A), the unsaturated monomer (B), the thermoplastic resin (C), the polyisocyanate (D), and the polymerization initiator (E) are mixed and dispersed using a mixer such as an ordinary mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder, and the carbon fibers (F) are mixed and dispersed in the obtained resin composition, as in the method for producing the SMC.
  • aging is preferably performed at a temperature of 25 to 60°C.
  • the molded article of the present invention is obtained from the fiber-reinforced molding material, and from the viewpoints of excellent productivity and excellent design diversity, the molding method is preferably heat compression molding of SMC or BMC.
  • a predetermined amount of a molding material such as SMC or BMC is weighed, placed in a mold heated to 110 to 180°C in advance, clamped by a compression molding machine to shape the molding material, the molding material is cured by maintaining a molding pressure of 0.1 to 30 MPa, and then the molded article is taken out to obtain a molded article.
  • a molding material such as SMC or BMC
  • a molding condition in which a molding pressure of 1 to 10 MPa is maintained at a mold temperature of 120 to 160°C in the mold for 1 to 2 minutes per the thickness 1 mm of the molded article is preferable, and a molding condition in which a molding pressure of 1 to 10 MPa is maintained at a mold temperature of 140 to 160°C for 30 to 90 seconds per the thickness 1 mm of the molded article is more preferable because productivity is further improved.
  • the molded article obtained from the fiber-reinforced molding material of the present invention is excellent in dimensional accuracy, bending strength and the like, and emission of volatile organic compounds is suppressed, the molded article can be suitably used in automotive members, railroad vehicle members, airspace craft members, ship members, house facility members, sports members, light-weight vehicle members, construction and civil engineering members, case bodies for OA instrument, and the like.
  • the hydroxyl value was determined by measuring the number of milligrams of potassium hydroxide (mgKOH/g) required to neutralize acetic acid generated when the resin sample 1 g was reacted at a specified temperature for a specified time using an acetylating agent based on a prescribed method in accordance with JIS K-0070.
  • the epoxy equivalent was calculated using a prescribed calculation formula, based on a prescribed method in accordance with JIS K-7236, by dropping perchloric acid to a resin sample in the co-presence of the sample and an ammonium bromide salt, and setting a point at which the generated hydrogen bromide became excessive by consuming all epoxy groups as an end point.
  • the mixture was cooled to around 60°C, 228 parts by mass of methacrylic acid and 0.29 parts by mass of t-butylhydroquinone were charged, and the mixture was heated to 90°C under a gas flow of a mixture of nitrogen and air at a ratio of 1:1. Then, 0.23 parts by mass of 2-methylimidazole was added thereto, and the mixture was heated to 110°C and reacted for 10 hours. As a result, the acid value became 6 or less, and the reaction was terminated. After cooling to around 60°C, the mixture was taken out of the reaction vessel to obtain a vinyl ester (A-1) having a hydroxyl value of 204 mgKOH/g.
  • the resin composition (X-1) obtained above was coated on a laminate film of polyethylene and polypropylene in an average coating amount of 1 kg/m 2 , and carbon fibers obtained by cutting a carbon fiber roving ("T700SC-12000-50C" manufactured by Toray Industries, Inc.) into 12.5 mm (hereinafter abbreviated as carbon fibers (F-1)) were uniformly dropped thereon from the air so as to have no fiber orientation, a uniform thickness, and a carbon fiber content of 47% by mass.
  • carbon fibers (F-1) carbon fibers
  • the carbon fibers were sandwiched between films coated with the resin composition (X-1) to impregnate the carbon fibers with the resin, and then left to stand in a thermostat at 45°C for 24 hours to obtain a sheet-shaped fiber-reinforced molding material (1).
  • the basis weight of the sheet-shaped fiber-reinforced molding material (1) was 2 kg/m 2 .
  • a resin composition (X-2) and a fiber-reinforced molding material (2) were obtained in the same manner as in Example 1, except that 20 parts by mass of the polyethylene fine powder used in Example 1 was changed to 20 parts by mass of a styrene-divinylbenzene copolymer ("SGP-70C” manufactured by Soken Chemical & Engineering Co., Ltd., solubility in phenoxyethyl methacrylate at 23°C: 0.1 g/100 g or less).
  • SGP-70C styrene-divinylbenzene copolymer
  • the molar ratio (NCO/OH) in the resin composition (X-2) was 0.74, and the basis weight of the fiber-reinforced molding material (2) was 2 kg/m 2 .
  • a resin composition (RX-1) and a fiber-reinforced molding material (R1) were obtained in the same manner as in Example 1, except that the polyethylene fine powder used in Example 1 was not used.
  • the molar ratio (NCO/OH) in the resin composition (RX-1) was 0.74, and the basis weight of the fiber-reinforced molding material (R1) was 2 kg/m 2 .
  • a resin composition (RX-2) and a fiber-reinforced molding material (R2) were obtained in the same manner as in Example 1, except that 45 parts by mass of phenoxyethyl methacrylate used in Example 1 was changed to 45 parts by mass of styrene and the polyethylene fine powder was not used.
  • the molar ratio (NCO/OH) in the resin composition (RX-2) was 0.37, and the basis weight of the fiber-reinforced molding material (R1) was 2 kg/m 2 .
  • the sheet-shaped fiber-reinforced molding material obtained above was subjected to pressure molding under molding conditions of a mold temperature of 140°C, a pressing time of 3 minutes, and a pressing force of 10 MPa at a charge ratio of 50% with respect to the projected area of the 30-cm square mold to obtain a flat molded article having a plate thickness of 2 mm.
  • the molded article obtained above was allowed to stand for 24 hours without being corrected, one point of the end portion of the molded article was fixed, the maximum height of the other end portion that was warped upward was measured, and the dimensional accuracy (amount of warpage deformation) was evaluated according to the following evaluation criteria.
  • Comparative Examples 1 and 2 are examples not containing the thermoplastic resin which is an essential component of the present invention, and it was found that the amount of warpage deformation was large and the dimensional accuracy was poor.

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Claims (5)

  1. Faserverstärkte Formmasse, umfassend: als wesentliche Rohmaterialien einen Vinylester (A), der ein Reaktionsprodukt eines Epoxyharzes (a1) mit einem Epoxyäquivalent im Bereich von 180 bis 500 und einer (Meth)acrylsäure (a2) ist; ein ungesättigtes Monomer (B) mit einem Flammpunkt von 100°C oder höher; ein thermoplastisches Harz (C); ein Polyisocyanat (D); einen Polymerisationsinitiator (E); und Kohlenstoffasern (F) mit einer Faserlänge von 2,5 bis 50 mm, wobei das thermoplastische Harz (C) eine Löslichkeit in dem ungesättigten Monomer (B) bei 23°C von 1 g/100 g oder weniger aufweist, das Massenverhältnis ((A)/(B)) des Vinylesters (A) zu dem ungesättigten Monomer (B) im Bereich von 40/60 bis 85/15 liegt, und das Molverhältnis (NCO/OH) der Isocyanatgruppe (NCO) des Polyisocyanats (D) zu der Hydroxygruppe (OH) des Vinylesters (A) im Bereich von 0,25 bis 0,85 liegt, und wobei der Flammpunkt nach der in JIS K2265-4:2007 definierten Cleveland-Open-Cup-Methode gemessen wird.
  2. Faserverstärkte Formmasse nach Anspruch 1, wobei das ungesättigte Monomer (B) Phenoxyethylmethacrylat und/oder Benzylmethacrylat ist.
  3. Faserverstärkte Formmasse nach Anspruch 1 oder 2, wobei das molare Verhältnis (COOH/EP) der Epoxidgruppe (EP) des Epoxidharzes (a1) zur Carboxylgruppe (COOH) der (Meth)acrylsäure (a2) im Bereich von 0,6 bis 1,1 liegt.
  4. Faserverstärkte Formmasse nach einem der Ansprüche 1 bis 3, wobei das Polyisocyanat (D) ein aromatisches Polyisocyanat ist.
  5. Geformter Gegenstand, der die faserverstärkte Formmasse nach einem der Ansprüche 1 bis 4 enthält.
EP18879026.5A 2017-11-20 2018-10-30 Faserverstärktes formmaterial und formkörper damit Active EP3715405B1 (de)

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US20220227913A1 (en) * 2019-05-16 2022-07-21 Dic Corporation Fiber-reinforced molding material and molded article using same
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WO2023089999A1 (ja) * 2021-11-18 2023-05-25 Dic株式会社 ラジカル硬化性樹脂組成物、繊維強化成形材料、及びそれを用いた成形品

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US5342554A (en) * 1993-01-07 1994-08-30 Gencorp Inc. Vinyl-terminated polyesters and polycarbonates for flexibilizing and improving the toughness of compositions from unsaturated polyesters and fiber reinforced plastics made from them
JP2005247879A (ja) 2004-03-01 2005-09-15 Showa Highpolymer Co Ltd 繊維強化複合材料用組成物及びその成形材料
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JP4385226B2 (ja) * 2004-11-29 2009-12-16 Ｄｉｃ株式会社 成形品用ラジカル重合性樹脂組成物及び繊維強化プラスチック成形品
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